Process for treating hydrocarbon oils



May 16, 1933. J. A. SCHAEFFER ET AL 1,908,924

PROCESS FOR TREATING HYDROCARBON OILS Fiied Feb. 29. 1932 INVENTOR Jean AdoM/e Sabaeffar BY Georges Pfersah ATTNEYJ' Patented May 16, 1933 UNITED STATE/IS;

PATENT OFFICE JEAN ADOLPHE SCHAEFFER AND GEORGE PFERSCH, OF BEYNES FRANCE, ASSIGNORS TO COMPAGNIE TECHNIQUE DES PETROLES, OF PARIS, FRANCE, A. CORPORATION OF FRANCE PROCESS FOR TREATING HYDROCABBON OILS Application. filed February 29, 1932, Serial No. 595,927, and in France September 23, 1930.

This invention relates to processes for treating oils and other liquids, particularly for mixing hydrocarbon, vegetable or other oils with acid or other reagents and to prod ucts derived therefrom. An apparatus which may be employed to carry out this process is also described but not claimed herein. Claims for this apparatus are contained in a copending application, Ser. No. 595,926 filed February 29, 1932.

In current practice in treating oils such as mineral hydrocarbon oils with acid, the oil and acid'are agitated and then allowed to separate by gravity. The action between acid and lubricating oils is relatively long when this method is used. Furthermore the treatment is uneconomical, entailing con siderable unnecessary loss of oil and acid. In addition it is a batch process and not continuous.

The principal object of the present invention is accordingly to provide a' simple process of the kind described capable of efiiciently treating oils and other liquids with diiiiculty miscible reagents and especially in the case of mineral hydrocarbon oils, of eliminating at least in part the disadvantages mentioned above; and to produce novel products of the type mentioned.

This application is a continuation in part of our copending application Ser. No. 513,733, filed February 5, 1931. The French application corresponding to Ser. No. 513,733 was filed in France September-23, 1930, this being the. earliest filed foreign application corresponding thereto.

The invention comprises the novel products as well as the novel processes and steps of processes according to which such prodnets are manufactured, the specific embodiments of which are described hereinafter by way of example and in accordance with which we now prefer to practice the invention.

Further and more specific objects, features and advantages clearly appear from the detailed description given below. The accompanying drawing which forms a part of this specification, illustrates by way of. exam le an apparatus which may be employed or carrying out an embodiment of the process.

50 Fig. 1 represents a diagrammatic elevation of a preferred embodiment of the invention. Fig. 2 represents a detail view of one of the oil spray nozzles. Fig. 3 represents a detail View of one of the acid spray nozzles.

Referring now particularly to the drawing, 1 indicates a substantially cylindrical chamber for mixing and settling oil and acid. The oil is introduced through a series of oil atomizers designated as 2, which are circumferentially spaced near the upper edge of the cylinder at about equidistance from one another. Centrally disposed on the top of the chamber 1 is an acid atomizer 3. Atomizers 2 and 3 are located as shown in the outermost heads of drumshaped hoods 4 and 5 respectively, the opposite end of each hood communicating directly with the interior of the chamber 1, The nozzles 2 are of a special type as shown in greater detail Fig. 2. Each comprises a hollow cylindrlcal body 2a which is separated from a chamber 2b by means of a diaphragm 20. The

liquid forced through pipe 2e under the effect of pressure can only escape to chamber 22') through a row of slots 2; which are not perpendicular to the axis but tangentlal. The liquid passing through these slots thus acquires a quick revolving motion, and the square cm. It comprises the following parts: A hollow cylindrical body 36 terminated by a, hollow cone 3e has two openings. Through opening 3a"the-liquid to be atomized is forced by pressure and 3d is the only outlet which consists in an annular slot limited between the cortical button 30 and the edges of the concentrical hollow cone 36. The width of the annular slot 3d is adjustable with a screw 3} by means of which the button 30 can be set more or less close to the edges of the hollow cone3e. Another annu- 100 mm. in diameter.

lar slot 39 terminates concentrical space 3]: limited between the hollow cone 3e and the hollow cone 32'. -Compressed air introduced results below, although we believe that a variation in range of particle size produced thereby \is permissible. It is preferable that the size of the reacting particles be not so large as to cause loss of oil and acid to vary to any considerable extent from that described below.

The nozzles 2 are directed inwardly and downwardly so that their axes projected form the elements of a cone while the center acid spray is along the longitudinal axis of the cone. The dimensions of this cone may be varied but as shown in Fig. 1 the axes meet at about one-third of the height of the chamber 1 from the top thereof. The atomizers 2 and 3 produce in the chamber .a mixture of acid and oil fogs. The particles of this fog mixture are so fine that there is almost an immediate contact between all of the acid and all of the oil to form a substantially homogeneous mixture thereof, and as this fog descends in the chamber 1 it tends to settle out and deposit particles of liquid therefrom. This liquid collects in the bottom of the chamber 1 and rises to about the level there shown.

.Air is supplied to the nozzle 3 through the line .6 under pressure of approximately 0.5 kg. per square cm., being passed through the air sieve 7 to remove particles which might block the nozzle.

This air passes out of the chamber 1 through a pipe 8 leading to an air filtr chamber 9 filled with Raschig rih gs 10 or similar material to prevent the outflow of liquid therewith. The acid supplied to nozzle 3 is driven through an acid line 11 by pump 12.

It passes through an acid filter 13 to removeany particles which might clog the nozzle 3.

The oil passes through a pipe line 14 to the nozzles 2 being forced through the line by pump 15. The pumps 12 and 15 are proportionating pumps-,that is they may be ad-- brine, or other temperature-regulating medium, in order to heat or cool the oil as desired. A control float 18 controls a by-pass valve'19' in a line 20 to by-pass the pump 15. This float member is in a chamber 21 connected by line 39, being pumped by 'pump a pipe 22 with a short well 23 running from the bottom of chamber 1. The liquid rises in the chamber 21 to the same height as in chamher 1 and the fioat 18 floats on the top of this liquid. It is connected by a suitable means,

L such as a chain, to an arm operating the valve 19 and in case the level of the liquid becomes too high in chamber 1 and correspondingly in chamber 21, the valve opens so as to allow liquid to pass through the pipe 20 to'by-pass the pump and reduce the amount of oil passing to the sprays 2.

From the lower part of the well 23 through pipe line 24 the liquid passes through a pump 25 and to reaction chambers 26 and 27. Pump 25 is connected on the same shaftwith pumps 12 and 15, which are set to deliver respectively acid and oil to the sprays in proper proportion and pump 25 being correspondingly set to pump away the acid-oil mixture. Each of the reaction chambers consists of an upright hollow cylinder with a motor 28 in a cap thereon. The lower end of the motor shaft has a gear 29 which meshes'with a gear on top of shaft 32, which in turn through gear 30 which meshes with gear 31 operates shaft 33. On both shafts are mounted circular bands 34 and 35 respectively. Rings 34 are mounted at right angle with respect to the rings 35 so that they will not interfere with one another on rotation and will provide sufiicient motion to prevent substantial settling of the oil-acid mixture pumped into to carry the liquid in a rotating motion, is

annihilated by the other one, and any centrifuging eifect is thus avoided, which would otherwise tend to throw heavier particles suspended in the liquid against the walls of the chamber. The speed of rotation of these rings 34 and 35 is approximately 200 to 400 R. P. M.

Liquid passes from the reaction chamber 26 to chamber 27 by pipe 36. From reaction chamber 27 it may pass by pipe 37 to a reaction and insolubilizingvochamber 38. This chamber is supplied with water through a w 40. The amount of water is suitably regulated. The chamber 38 is also provided with a motor 28 and gear driven shafts 32 and 33 provided with rings 34 and 35 as in the case of the other reaction chamber.

The mixture passing from the insolubilizing chamber by pipe 41 passes to'a centrifugal separator 42 running at high speed about 14000 R. P. M. Acid-refined oil passes out of the pipe 43 and acidsludges pass out of the p pe The process which we prefer to carry out' in this apparatus is as follows"":-'+Oil (for example a lubricating oil having a viscosity of 400" Saybolt Universal-viscosimeter at 100 F.) is heated to 80 F. by the heat exchanger 16 and is introduced underf'pump pressure through the sprays 2 at the rate of about 9 gals. per minute. .The, sprays deliver a fine smoke or fog into the fchamber 1 and are :net therein by the fine -smoke or fog resulting from the spraying 'of sulfuric acid,

for example 96% H SO or other like refining reagent passing from the spray 3. Sulfuric acid of this strength for the treatment of the above oil is preferably passed through the spray at the rate of 0.2 gals. per minute. The fog of the mixed acid and oil descends and settles as a liquid in the bottom of the chamber, the air passing out of the chamber and away from the acid mixture. At this point in the process if a test tube of the mixture of acid and oil be taken, it will show a substantially homogeneous liquid, that is, there will not be any apparent stratification of any sulfuric acid and oil or the presence of insoluble products in suspension detectable by the naked eye.

In theform just mentioned it appears that the sulfuric acid and oil have assumed practically the formof a homogeneous solution and reaction between the materials to produce a sludge containing asphalt, coloring material, etc., should now be allowed to take place. We allow this reaction to take place for the production of these products while substantially preventing the settlin out of the insoluble products. This is done y passing the acid or mixture to one or more reaction chambers 26, 27 and 38, through which the liquid slowly passes, occupying a sufficient interval to allow the reaction between tioned above, the time of passage through the reaction zone or reaction chambers is approximately 10 minutes.- Having passed through the reaction chambers, the material may pass through the insolubilizing reaction 4 chamber 38 in which water is added to it at the rate of approximately 0.06 kg. per minute. This results in the final insolubilization of the asphalt and other products to be sepa rated and the material is now ready to be separated which is done by passing it to a separator having a speed of approximately 14000 R. P. M. As shown the acid oil passes out separately from the asphaltic and other constituents. a

The above description has been made in connection with a specific oil run under spe- I cific conditions. It is to be understood that the description is illustrative of the process and the process is not confined to the details there given. The strength of the sulfuric acid may vary from 10 to 100% by weight of H SO content, or even fuming sulfuric acid may be used. The oils may be of various types viz. gasoline, kerosene, transformer oils, spindle oils, neutral oils, machine oils, motor oils, cylinder oils, and the like.

We have obtained successful results with temperatures of the untreated oils ranging as low as 30 F. to as high as 160 F. The period for reaction in the reaction chamber or chambers will vary also according to the type of oil and this may be controlled by the rate of umping.

ther reagents may be employed such as sulfuric acid and in place of hydrocarbon oils vegetable oils or others to be subjected to reaction with such reagents may. be used.

After the reaction between the oil and reagent, it is important that impurities be separated rapidly from the treated oil. For this purpose We employ, as indicated, a separation by centrifuge or we may submit the treated liquid to shock or any other force exercising a rapid separating effect on liquids of different densities, as set forth in copending application Ser. No. 513,7 33, filed Feb. 5, 1931.

We have found that our process mentioned conserves time and expense, including particularly a marked lowering in oil losses and in amount of acid required. Below is given a table showing the results of tests onvarious' types of oil as compared with the results obtained by employing the old process in which the acid was brought into contact with the oil in two dumps with intermediate settling. The acid employed in all of these tests contained 96% H 80 The table is as follows:

C. T. P. industrial Conventional intreatment dustrial treatment Original oil Viscosity Per; shiat- Per; 'Rpcan cen su tof ing of g i ing acid NPA acid NPA used color used color Transior- 108" S. U. 9 2.8 1% 12 10 1% met ail. at 100 F.

(transformer oil).

Lubricating 200" S.U.at 3 5 4% 8 14 4% neutral 100 F. oil.

Lubricating 120"S.U. at 3.25 5.6 2% 8 7 3 spindle 100 F. oil.

Lubricating 220" S.U.at 2 4.5 3% 8 10.5 3%

neutral 100 F. I oil.

Lubricating 235 S.U.at 2 5. 7- 4 8 10. 3%

neutral 100 F. 3 6. 2 3% oil. I 4 6.4 2%

Lubricating 3W'S.U-.at 2 5 4% 8 13 4% machine 100 F. oil.

Lubricating 4017' S.U. at 3 7 4 8 13 3% machine 100 F. 4 54 3% oil. 5 .84- 3 Motoroil. 79" S.U. at 3 6.2 4% 5.5 12 4% Savings on the acid range from 30 .to 7

- ofthe consumption as compared with the con- U ered when using the conventional process.

The oils obtained are acid oils free from substantially all insoluble particles resulting from the reaction. The acid index of these oils is low and is such that they may be immediately neutralized and decolorized with clay; or even the clay treatment by contact without neutralization may be employed without additional settling. The process is continuous enabling the treatment of large iquantities of material in a relatively small ime.

As stated above the apparatus which we prefer to employ in carrying out this process is as described above. In practice we find it inexpensive to install and operate and highly efiicient in action. It is capable of continuousoperation'and with its compact form is able to handle large quantities of material in a relatively small space.

Although we have described the feed from the well of the mixing chamber'l as carried on by a pump and the supply of the water for insolubilization in the insolubilizing machine as also under pressure, it will be noted that the flow of materials through the reaction and insolubilizing chambers and to the separator may be carried on by gravity if deslred. v While 'we have described our improvements in great detail and with respect to certain preferred embodiments thereof, we do not desire to be limited to such details or embodiments since many changes and modifications may be made and the invention embodied in widely diflerent forms without departing from the spirit and scope thereof in its broader aspects. Hence we desire to cover all equivalents and all modifications and forms coming within the language or scope of any one or more of the appended claims.

The term difliculty miscible liquid reagent employed in the claims is intended to include chemical reagents normally liquid at room temperature capable of reacting with the hydrocarbon oil to chemically change certain constituents thereof. It includes refining agents such as sulphuric acid, phosphoric acid and other liquid agents well known to those skilled in the art.

What we claim as new and desire to secure by Letters Patent is I 1. The steps in the process for treating hydrocarbon oil with a diflicultly miscible liquid reagent which comprises atomizing said oil and reagent into a space sufiicient to permit atomization to form a-fog admixture, form- I ing a liquid containing said oil and reagent from said fog. and separating said oil from said reagent toprevent prolonged reaction. 2. Aflprocess for treating an oil with a diflicultly miscible liquid reagent which comprises atomizin into a space su cient to permit atomization and to form a fog admixture, settling said fog in said space to form a liquid containing said oil and reagent, retaining the oil and reagent in said space for a predetermined interval and separating the oil from the products of reaction. 1-

3. A process for treating a hydrocarbon oil with acid which comprises atomizing hydrocarbon oil and acid into a space suficient to permit atomization and to form a substantially homogeneous admixture thereof, settling said oil and acid in said space, withdrawing said oil and acid into a chamber, retaining said oil and acid in said chamber for a predetermined interval and separating the oil from the acid sludge. I

4. A process according to claim 3 in which an insolubilizing agent is introduced into the oil and acid mixture prior to the separation of the oil from the acid sludge.

5. A process for refining oils which comprises bringing together a fog of sulfuric acid and a fog of impure hydrocarbon oil settling a substantially homogeneous liquid mixture therefrom, agitating the liquid while allowing reaction between the sulfuric acid and hydrocarbon oil to occur to avoid substantially. settling out of asphaltic coloring said oil and said reagent material and the like and centrifugally separating the said asphaltic coloring materials and the like from the substantially impure oil.

6. A process according to claim 5 in which water is added during the course of the reaction to produce insolubilization of constit-f uents in the oil.

7. A process according to claim 5 in which the acid employed is concentrated sulfuric acid containing a'H SO content of above' approximately 62%. 1

8. A process according to claim 5 in which .the sizeof the acid and oil particles is from ents is about 10 minutes.

In testimony whereof we have signed our names to this specification.

JEAN ADOLPHE SCHAEFFER. GEORGE PFERSCH.

r 5 CERTIFICATE or CORRECTION.

Patent No. 1,908,924. May 16, 1933.

JEAN ADOLPHE SCHAEFFER, ET AL.

It is hereby certified that the name of the co-inventor in the above numbered patent was erroneously written and printed as "GEORGE PFERSCH" whereas said name should have been written and printed as "GEORGES PFERSCH" as shown by the records of the case; page ,1, line 23, and line 46, page 4, for "difficulty" read "diffieultly"; page 3, line 119, column 7 of the table, for "10." read "10.5"; and that the said Letters Patent should be'read with these corrections therein that the same may conform to the record of the ease in the Patent Office Signed and sealed this 15th day of August, A. D. 1933.

M. J. Moore.

(Seal) Acting Commissioner of Patents. 

